CN113912023A - Preparation method of sodium ion battery negative electrode material - Google Patents
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Abstract
The invention discloses a preparation method of a sodium ion battery cathode material, which comprises the following steps: dissolving chitosan in a mixed solution of glacial acetic acid and deionized water, and stirring; step two, ultrasonically dissolving transition metal cyanate in deionized water, and then adding the solution in the step one to obtain a transition metal cyanate solution; after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly performing freeze drying to obtain a precursor; sintering the precursor at 600-700 ℃, cleaning and vacuum drying; and step five, mixing and sintering the product obtained in the step four and selenium powder at 300-400 ℃ to obtain the nitrogen-doped porous carbon transition metal selenide sodium ion battery cathode material. The preparation method is simple to operate and low in cost; the prepared nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material has high cycle performance and good rate capability.
Description
Technical Field
The invention relates to a preparation method of a battery cathode material, in particular to a preparation method of a sodium ion battery cathode material.
Background
With the continuous upgrade of energy crisis, the heat pump systemIn view of the limited resources and increased cost of lithium, Lithium Ion Batteries (LIBs) are almost unable to meet the ever-increasing energy demands of modern society. Sodium Ion Batteries (SIBs) are used as substitutes for LIBs, and have a wide application prospect due to low cost, abundant resources and environmental friendliness. However, due to its large radius (Na)+vs Li+0.102nm vs 0.076nm) and a heavier molar mass (Na)+vs Li+It was 22.99vs 6.94gmol-1)，Na+Ion diffusion ratio in electrode material Li+It is more difficult. In addition, the electrode material has large volume change, low specific capacity, low rate capability and poor cycle stability in the discharging/charging process, and the application of the SIBs is obviously influenced. Therefore, it remains a great challenge to suppress the volume change during discharge/charge and further improve the conductivity of electrode materials of high-performance SIBs.
Transition metal diselenides, e.g. MoSe2、CoSe2、FeSe2And the like, have received considerable attention as a promising anode material due to its high theoretical capacity and wide availability. Wherein, FeSe2Due to abundant resources, low toxicity, high theoretical performance and environmental friendliness, the method has attracted extensive attention of people. However, like other transition metal diselenides, FeSe2The development of (b) is limited by large volume changes during discharge/charge, resulting in structural instability and thus a severe drop in capacity, and a drop in rate performance due to electrode pulverization and particle aggregation. Much effort has been made to overcome these problems, and FeSe has been used2Encapsulation into a carbon matrix is considered an effective method. For example, FeSe prepared by Zhang et al (ACS appl. Mater. interfaces 8(2016)13849)2The microspheres are dispersed in the sulfur-doped reduced graphene oxide sheet, and have excellent electrochemical performance as a promising SIBs negative electrode. The results show that FeSe is present during the continuous sodium insertion/extraction process2The combination with carbon can inhibit volume expansion and improve electrochemical performance. CoSe2Has good electron transfer capacity, and has a theoretical capacity of 494mAhg as SIBs anode-1Significantly greater than graphite (35 mAhg)-1). However, sodium ions are inThe slow charge movement and high intrinsic resistance during the insertion and extraction process greatly limit the performance of the SIBs cathode.
Without the protection of carbon, the transition metal selenide active material on the electrode material can face larger volume expansion and even structure collapse in the charging and discharging processes, thereby causing great influence on the performance of the battery. At present, a solvothermal method is mostly adopted to prepare a precursor material of a transition metal selenide sodium-ion battery cathode material in a high-temperature and high-pressure environment, and then high-temperature selenization is carried out. The reaction conditions of high temperature and high pressure bring potential dangers, and the reaction condition is not convenient to observe directly because the reaction system is in a closed container.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide the preparation method of the sodium-ion battery cathode material, which is simple to operate, short in period and low in cost.
The technical scheme is as follows: the preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
dissolving chitosan in a mixed solution of glacial acetic acid and deionized water, and stirring;
ultrasonically dissolving transition metal cyanate in deionized water, and then adding the solution in the step one to obtain a transition metal cyanate solution, so as to generate gelatinous complex precipitates, and generate complexes with different colors by using different transition metal ions;
after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly performing freeze drying to obtain a precursor;
sintering the precursor at 600-700 ℃, cleaning and vacuum drying;
and step five, mixing and sintering the product obtained in the step four and selenium powder at 300-400 ℃ to obtain the nitrogen-doped porous carbon transition metal selenide sodium ion battery cathode material.
Further, in the first step, the mass-to-volume ratio of the chitosan to the mixed solution of glacial acetic acid and deionized water is 5-10 mg/mL. The mass fraction of the glacial acetic acid in the mixed solution of the glacial acetic acid and the deionized water is 20-25%, and the preferred mass fraction is 25%. The stirring speed is 400-600 r/min, and the stirring time is 18-24 h.
Further, in the second step, the transition metal cyanate is one or more of potassium ferricyanide, potassium ferrocyanide, potassium cobalt cyanide and potassium nickel cyanide. Preferably, the transition metal cyanate is potassium ferricyanide or potassium cobaltcyanide. The concentration of the transition metal ions in the transition metal cyanate solution is 0.5 to 1.0 mol/L.
Further, in the third step, the freeze drying time is 24-48 h, and the temperature is-80 to-60 ℃. The temperature of freeze drying is lower than-80 ℃, and the water capturing capacity of the cold trap is not obviously improved; the freeze-drying temperature is higher than-60 ℃, and a delamination phenomenon, i.e. an unevenness in the upper and lower parts, may occur.
Further, in the fourth step, the temperature rising rate of sintering is 3-5 ℃/min, and the heat preservation time is 2-3 h. The temperature of vacuum drying is 60-70 ℃, and the time is 8-12 h.
Further, in the fifth step, the mass ratio of the product obtained in the fourth step to the selenium powder is 1: 2-3, the heating rate of the mixed sintering is 2-3 ℃/min, and the heat preservation time is 2-3 h.
The preparation principle is as follows: the nitrogen-doped porous carbon structure remarkably improves the specific surface area of the transition metal selenide negative electrode material, greatly increases the contact area between electrolyte and the surface of an electrode, provides more reactive sites, can buffer the volume change of the electrode material in the charge-discharge process, shortens the path of ion transmission, and is beneficial to ensuring the structural integrity of the electrode material, thereby improving the cycle performance and the rate capability of the nitrogen-doped porous carbon transition metal selenide sodium ion battery negative electrode material. In addition, -NH with activity in the chitosan molecule2The side group can form a complex with transition metal ions, and the complex is tightly combined together by virtue of a coordination bond, so that the stability of the material structure is enhanced, and the long-cycle stability is guaranteed.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. the preparation method is simple to operate and low in cost, the precursor of the electrode material is dried in a frozen state, the physical structure and molecular structure of the material are changed little, and the organization structure and appearance form of the material are well preserved;
2. the prepared nitrogen-doped porous carbon transition metal selenide sodium ion battery cathode material is prepared by mixing 10Ag-1Sometimes 361mAhg-1Capacity of (2), 50Ag-1Still has 320mAhg-1Has excellent capacity and rate performance, and still has 494mAhg after 1000 cycles-1Has good circulation stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a product obtained in example 1 of the present invention at a magnification of 5 ten thousand times;
FIG. 3 is a scanning electron microscope image of the product obtained in example 1 of the present invention at 8 ten thousand times magnification;
FIG. 4 is a graph showing the cycle profile of the product obtained in example 1 of the present invention;
FIG. 5 is a graph of rate capability of the product obtained in example 1 of the present invention.
Detailed Description
Example 1
A preparation method of a sodium-ion battery negative electrode material comprises the following steps:
(1) dissolving 200mg of chitosan into a mixed solution of 5mL of glacial acetic acid and 15mL of deionized water, and stirring at a stirring speed of 500r/min for 24h, wherein the mass fraction of the glacial acetic acid in the mixed solution is 25 wt%;
(2) ultrasonically dissolving 0.5mmol of potassium ferricyanide and 0.5mmol of potassium cobalt cyanide in 2mL of deionized water, and then adding the deionized water into the solution obtained in the first step to obtain a transition metal cyanate solution; (3) after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly carrying out freeze drying at-60 ℃ for 24h to obtain a precursor;
(4) sintering the precursor at 700 ℃, wherein the heating rate is 5 ℃/min, the heat preservation time is 2h, cleaning the product for 5 times, and then carrying out vacuum drying at 60 ℃ for 12 h;
(5) and (3) mixing and sintering the product obtained in the step (4) and selenium powder at 400 ℃ according to the mass ratio of 1:2, wherein the heating rate is 3 ℃/min, and the heat preservation time is 3h, so as to obtain the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material.
FIG. 1 is an X-ray diffraction pattern of the product obtained in this example, and from X-ray powder diffraction peaks, FeSe was successfully synthesized2/CoSe2-CN。
FIG. 2 is a scanning electron micrograph (5 ten thousand times) of the product obtained in this example, which shows that the sample obtained in this example is a sheet structure with a length and a width of about 1 μm, and the surface of the sample has a uniform pore structure.
FIG. 3 is a high power (8 ten thousand times) SEM image of the product obtained in this example, from which FeSe of nitrogen-doped porous carbon can be seen2/CoSe2The aperture size of CN is 25nm-40 nm.
FIG. 4 is a graph showing the cycle curve of the product obtained in this example for sodium sheet half cell at 1Ag-1The first discharge capacity is 477mAhg-1After 1000 cycles, 494mAhg still exists-1The capacity (c) shows an upward trend, and exhibits excellent cycle performance.
FIG. 5 is a graph of rate capability of the product obtained in this example for sodium sheet half cell, 10Ag-1Sometimes 361mAhg-1Capacity of (2), 50Ag-1Still has 320mAhg-1The capacity of (a) shows excellent rate capability.
Example 2
A preparation method of a sodium-ion battery negative electrode material comprises the following steps:
(1) dissolving 100mg of chitosan into a mixed solution of 5mL of glacial acetic acid and 15mL of deionized water, and stirring at a stirring speed of 600r/min for 18h, wherein the mass fraction of the glacial acetic acid in the mixed solution is 20 wt%;
(2) ultrasonically dissolving 2mmol of potassium ferrocyanide in 2mL of deionized water, and then adding the solution into the solution obtained in the first step to obtain a transition metal cyanate solution;
(3) carrying out ultrasonic dispersion on a transition metal cyanate solution, and then quickly carrying out freeze drying at-80 ℃ for 48h to obtain a precursor;
(4) sintering the precursor at 600 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 3h, cleaning the product for 5 times, and then drying the product in vacuum at 70 ℃ for 8 h;
(5) and (3) mixing and sintering the product obtained in the step (4) and selenium powder at 300 ℃ according to the mass ratio of 1:3, wherein the heating rate is 2 ℃/min, and the heat preservation time is 2h, so as to obtain the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material.
Example 3
A preparation method of a sodium-ion battery negative electrode material comprises the following steps:
(1) 160mg of chitosan is dissolved in 5mL of glacial acetic acid and 15mL of deionized water mixed solution, and stirred for 20 hours at the stirring speed of 450r/min, wherein the mass fraction of the glacial acetic acid in the mixed solution is 23 wt%;
(2) ultrasonically dissolving 1.4mmol of potassium nickel cyanide in 2mL of deionized water, and then adding the solution in the first step to obtain a transition metal cyanate solution;
(3) carrying out ultrasonic dispersion on a transition metal cyanate solution, and then quickly carrying out freeze drying at-70 ℃ for 36h to obtain a precursor;
(4) sintering the precursor at 650 ℃, wherein the heating rate is 4 ℃/min, the heat preservation time is 2.5h, cleaning the product for 5 times, and then drying the product in vacuum at 65 ℃ for 10 h;
(5) and (3) mixing and sintering the product obtained in the step (4) and selenium powder at 350 ℃ according to the mass ratio of 1:2.5, wherein the heating rate is 2.5 ℃/min, and the heat preservation time is 2.5h, so as to obtain the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material.
Example 4
A preparation method of a sodium-ion battery negative electrode material comprises the following steps:
(1) dissolving 140mg of chitosan into a mixed solution of 5mL of glacial acetic acid and 15mL of deionized water, and stirring at a stirring speed of 400r/min for 22h, wherein the mass fraction of the glacial acetic acid in the mixed solution is 22 wt%;
(2) ultrasonically dissolving 1mmol of potassium ferricyanide and 0.6mmol of potassium nickel cyanide in 2mL of deionized water, and then adding the solution into the solution obtained in the first step to obtain a transition metal cyanate solution;
(3) after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly carrying out freeze drying at-65 ℃ for 30h to obtain a precursor;
(4) sintering the precursor at 620 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, cleaning the product for 5 times, and then carrying out vacuum drying at 63 ℃ for 9 h;
(5) and (3) mixing and sintering the product obtained in the step (4) and selenium powder at 320 ℃ according to the mass ratio of 1:2, wherein the heating rate is 2 ℃/min, and the heat preservation time is 2h, so as to obtain the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material.
Example 5
A preparation method of a sodium-ion battery negative electrode material comprises the following steps:
(1) dissolving 120mg of chitosan into a mixed solution of 5mL of glacial acetic acid and 15mL of deionized water, and stirring at a stirring speed of 550r/min for 21 hours, wherein the mass fraction of the glacial acetic acid in the mixed solution is 21 wt%;
(2) ultrasonically dissolving 0.8mmol of potassium ferrocyanide and 1mmol of potassium cobalt cyanide in 2mL of deionized water, and then adding the solution into the solution obtained in the first step to obtain a transition metal cyanate solution;
(3) after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly carrying out freeze drying at-75 ℃ for 40h to obtain a precursor;
(4) sintering the precursor at 670 ℃, wherein the heating rate is 5 ℃/min, the heat preservation time is 3h, cleaning the product for 5 times, and then drying the product at 67 ℃ for 11h in vacuum;
(5) and (3) mixing and sintering the product obtained in the step (4) and selenium powder at 390 ℃ according to the mass ratio of 1:3, wherein the heating rate is 3 ℃/min, and the heat preservation time is 3h, so as to obtain the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material.
Comparative example 1
TABLE 1 moles of Potassium ferricyanide and Potassium Cocyanoxide
| Sample number | Ⅰ | Ⅱ | Ⅲ | Ⅳ | Ⅴ |
| Potassium ferricyanide | 0.2mmol | 0.3mmol | 0.4mmol | 0.6mmol | 0.7mmol |
| Potassium cobalt cyanide | 0.8mmol | 0.7mmol | 0.6mmol | 0.4mmol | 0.3mmol |
This comparative example is identical to the rest of the procedure of example 1, except that: the molar numbers of potassium ferricyanide and potassium cobaltcyanide are shown in table 1 above, and the cycling performance and capacity of samples i-v are respectively tested, and compared with those of example 1, it can be found that: the molar ratio of 0.5mmol of potassium ferricyanide to 0.5mmol of potassium cobalt cyanide in example 1 is the optimum ratio.
Comparative example 2
1.2mmol of C4H6NiO4·4H2O and 1.5mmol C6H5Na3O7·2H2Dissolving O in 40mL of deionized water, then ultrasonically dispersing 30mg of CNTs in the solution, and stirring for 0.5h to form a solution A; adding 0.8mmol K3[Co(CN)6]Dissolving in 60mL deionized water, stirring for 0.5h to form solution B, adding solution B into solution A, and stirring the obtained mixed solution at room temperature for 24 h. And finally, washing, centrifuging and drying to obtain the Ni-Co-CNT composite material. Mixing Ni-Co-CNT and Se powder according to a mass ratio of 1:2, weighing, and placing the quartz boats at two ends respectively. Subsequently, the quartz boat was placed in a tube furnace and maintained at 500 ℃ for 2 hours. And naturally cooling to obtain the Ni-Co-Se-CNT composite material.
The battery performance test method was the same as in example 1. Ni-Co-Se-CNT electrode on 1Ag-1After circulating for 500 circles under the current density, the specific discharge capacity is 193.6mAhg-1。
In conclusion, the nitrogen-doped porous carbon transition metal selenide sodium-ion battery cathode material prepared by the invention has better electrochemical performance.
Claims (10)
1. The preparation method of the negative electrode material of the sodium-ion battery is characterized by comprising the following steps of:
dissolving chitosan in a mixed solution of glacial acetic acid and deionized water, and stirring;
step two, ultrasonically dissolving transition metal cyanate in deionized water, and then adding the solution in the step one to obtain a transition metal cyanate solution;
after the transition metal cyanate solution is subjected to ultrasonic dispersion, quickly performing freeze drying to obtain a precursor;
sintering the precursor at 600-700 ℃, cleaning and vacuum drying;
and step five, mixing and sintering the product obtained in the step four and selenium powder at 300-400 ℃ to obtain the nitrogen-doped porous carbon transition metal selenide sodium ion battery cathode material.
2. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the first step, the mass-to-volume ratio of the chitosan to the mixed solution of glacial acetic acid and deionized water is 5-10 mg/mL.
3. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the first step, the mass fraction of the glacial acetic acid in the mixed solution of the glacial acetic acid and the deionized water is 20-25%.
4. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the first step, the stirring speed is 400-600 r/min, and the stirring time is 18-24 h.
5. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the second step, the transition metal cyanate is one or more of potassium ferricyanide, potassium ferrocyanide, potassium cobalt cyanide and potassium nickel cyanide.
6. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the second step, the concentration of the transition metal ions in the transition metal cyanate solution is 0.5-1.0 mol/L.
7. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the third step, the freeze drying time is 24-48 h, and the temperature is-80 to-60 ℃.
8. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the fourth step, the temperature rising rate of sintering is 3-5 ℃/min, and the heat preservation time is 2-3 h.
9. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the fourth step, the temperature of vacuum drying is 60-70 ℃, and the time is 8-12 h.
10. The preparation method of the negative electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps: in the fifth step, the mass ratio of the product obtained in the fourth step to the selenium powder is 1: 2-3, the heating rate of the mixed sintering is 2-3 ℃/min, and the heat preservation time is 2-3 h.
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| CN114551868A (en) * | 2022-01-27 | 2022-05-27 | 常熟理工学院 | Sodium ion battery negative electrode material and preparation method thereof |
| CN114551868B (en) * | 2022-01-27 | 2024-04-19 | 常熟理工学院 | Negative electrode material of sodium ion battery and preparation method thereof |
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| CN114551868A (en) * | 2022-01-27 | 2022-05-27 | 常熟理工学院 | Sodium ion battery negative electrode material and preparation method thereof |
| CN114551868B (en) * | 2022-01-27 | 2024-04-19 | 常熟理工学院 | Negative electrode material of sodium ion battery and preparation method thereof |
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